Sucrose ethers



3,170,915 SUCROSE ETHERS Van R. Gaertner, Dayton, Ohio, assignor to Monsanto Company, a corporation of Delaware No Drawing. Filed Apr. 11, 1960, Ser. No. 21,120 16 Claims. (U. 26tl21t)) The present invention relates to the preparation of new ether compounds. More specifically this invention relates to others of non-reducing polyol-s, particularly sucrose. In one aspect, this invention relates to sugar type others as new compounds. In another aspect this invention relates to methods, for preparing sugar-type others from non-reducing polyols and alkyl, aikenyl, alkoxymethyl, and alkarylmethyl halides. In another aspect, this invention relates to surfactant compositions which have very high detersive properties as well as good wetting and lime soap dispersion efficiencies. In another aspect this invention relates to detergent compositions which contain readily biodegradable moieties.

High foaming synthetic detergent compositions have caused some concern to those in charge of sewage and industrial waste disposal and water treatment processes. Problems of excessive foaming as well as problems of chemical and biological balance in sludge, sewage, and water treatment plants have been attributed to the use of these materials. Because of this, the detergent producing industry has been looking for detergent materials which would not present waste disposal problems. A detergent material which is biodegradable would help eliminate or at least substantially minimize such disposal problems.

It is, therefore, an object of this invention to provide ew sugar type others as new compounds.

It is a further object of this invention to provide methods for preparing sugar type ethers from non-reducing polyols and alkyl, alkenyl, alkoxymethyl, and alkarylmethyl halides.

It is another object of this invention to provide surfactant compositions which have very high detersive properties as well as good wetting and lime soap dispersion efficiencies.

Another object of this invention is to provide detergent compositions which contain readily biodegradable active moieties.

Other aspects, objects, and advantages of this invention will be apparent from a consideration of the accompanying disclosure and the appended claims,

In accordance with this invention, a halogen compound having the general formula R-CH -X is reacted with a polyol of the group consisting of non-reducing disaccharide sugars and sugar alcohols having the general formula HOZ according to the following equation wherein X is a halogen selected from the group consisting of bromine, chlorine, and iodine, R is selected from the group consisting of alkyl radicals, alkenyl radicals having the olefinic double bond beyond the alpha position relative to the halogen atom or ether oxygen atom, and alkoxy radicals having from 8 to 24 carbon atoms, and alkaryl radicals having a total of from 14 to 24 carbon atoms and from 8 to 18 carbon atoms in at least one alkyl radical attached to the aryl ring, and OZ is the residue of the polyol selected from the group consisting of nonreducing disaccharide sugars and sugar alcohols with Z being linked to the methylene group through the oxygen atom of one of the hydroxyl groups of the polyol, in the presence of a basic material.

Further, in accordance with this invention, there are provided, as new compounds sugar-type ethers of the formula RCH OZ I United States Patent wherein R and Z are as defined above.

Further, in accordance with this invention there are provided new surfactant compositions comprising as the active ingredient an alkyl, alkenyl, alkoxymethyl, or an alkarylmethyl ether of a non-reducing polyol of the formula given above.

Further, in accordance With this invention there are provided new all purpose detergent compositions comprising a sodium, potassium, or ammonium salt of a longchain fatty acid and, as an essential ingredient, an alkyl, alkenyl, alkoxymethyl or an alkarylmethyl ether of a non-reducing polyol of the formula given above.

Further, in accordance with this invention, there are provided new biodegradable detergent compositions which contain as an essential active ingredient, an alkyl, alkenyl, alkoxymethyl, or an alkarylmethyl ether of a non-reducing polyol of the formula given above.

The compounds of this invention can be characterized as alkyl, alkenyl, alkoxymethyi, an alkarylmethyl ether of non-reducing disaccharide sugars and sugar alcohols.

Presently useful non-reducing disaccharide sugars and sugar alcohols include, e.g., sucrose, trehalose, rafiinose, mannitol, sorbitol, dulcitol, etc. Of these materials sucrose is the most important and is the preferred nonreducing sugar because it is readily available and is the most economical material to use.

Branched chain alkyl, alkenyl, alkoxymethyl, andalkarylmethyl chlorides, bromides, and iodides are preferred for the purposes of this invention. When alkyl halides are used or when alkenyl halides which have the double bond beyond the beta position relative to the halide atom are used, i.e., those wherein the double bond is farther along in the carbon chain than is as illustrated purposes of this invention, I have found that somewhat better yields of products may be obtained if a few crystals of an alkali metal iodide are stirred into the reaction mixture. Vinyl type alkenyl halides, i.e., those of the type are not within the scope of this invention. They do not react usefully with polyol compounds to form ether compounds. In the other types of halides that may be used, that is, in the fl-alkenyl halides, the alkoxymethyl halides, and in the alkarylrnethyl halides, the chlorides may be used as readily as the bromides, and iodides, Examples of alkyl halides that may be used to prepare the compounds of this invention are, e.g., the normal alkyl halides such as nonyl bromide, decyl iodide, dodecyl chloride, tridecyl bromide, hexadecyl iodide, octadecyl chloride, docosyl chloride, tricosyl bromide, pentacosyl iodide, and branched chain alkyl halides such as Z-et-hylhexyl chloride, 4,4,6-trimethyldodecyl bromide, etc. The preferred alkyl halides are branched chain alkyl halides, the branched chain alkyl radical of which is derived from branched chain alkanols having from 9 to 25 carbon atoms obtained via the 0x0 process by the high temperature, high pressure reaction of carbon monoxide, hydrogen, and branched chain olefins such as propylene trimer, propylene tetramer, butylene trimer, etc., as de scribed, for example, in U.S. Patents 2,820,067, issued January 24, 1958, and 2,638,487, issued May 12, 1953.

Alkenyl halides which may be used are, for example,

l-chloro-Z-octene, l-iodo-Z-dodecene, 1-bromo-4-nonene, 1-chloro-4-methyl-6-octene, 1-chloro-8-hexadecene, liodo-4-tetracosene, and branched chain alkenyl halides, such as are derived from branched chain alkenyl alcohols having from 9 to 25 carbon atoms, e.g., 2,4,6,8,10-pentamethyl-3-decenyl bromide, 2,2,4,6,6-pentamethyl-4-hexenyl iodide, and 2,4,6,8,10,12-hexamethyl-6-dodecenyl chloride.

Examples of alkoxymethyl halides that may be used for preparing the compounds of this invention are the normal alkyloxymethyl halides, e. g., heptyloxymethyl bromide, dodecycloxymethyl iodide, tridecyloxymethyl chloride, hexadecyloxymethyl bromide, etc., branched chain alkoxymethyl halides such as 2-ethylhexyloxymethyl chloride, 4,4,6-trimethyldecyloxymethyl bromide, 4-butyloctyloxymethyl iodide, etc., and alkoxymethyl halides where the alkyl portion of the halide is derived from branched chain alcohols, for example, as obtained by the Oxo process e.g., 2,4,6-trimethylhexyloxymethyl chloride, 2,4, 6,8,lO-pentamethyldecyloxymethyl bromide, and 2,2,4,4, 6,6-hexamethylhexyloxymethyl iodide, etc.

Examples of alkarylmethyl halides that may be used to prepare the ether compounds of this invention are: octylbenzylbromide, (2-ethylheptyl)benzyl chloride, tridecylbenzyl iodide, nonyltolylmethyl chloride, octylbutylbenzyl bromide, dinonylbenzyl, hexadecylethylbenzyl iodide, ot-(B-nonylnaphthyDmethyl bromide, (4-dodecyl xenyl)methyl chlorides; nonyltolylmethyl chloride, octylbutylbenzyl bromide, dinonylbenzyl chloride, hexadecylethylbenzyl iodide, l-(2-nonyl-4-methylnaphthyl)methyl chloride, etc., alkarylmethyl halides wherein the alkyl radical is a branched chain, e.g., decylbenzyl chloride wherein the decyl radical is derived from an alcohol obtained from propylene trimer, carbon monoxide, and hydrogen via the x0 process, a branched chain tride cylbenzyl bromide wherein the tridecyl radical is branched, and a branched chain a-(dodecylnaphthyl)methyl bromide wherein the dodecyl is derived for example from propylene trimer,

A few examples of the types of compounds prepared by the method of this invention are, e.g., the O-alkyl sugar and sugar alcohol ethers, such as O-(2-ethylhexyl)sucrose, O-dodecylsorbitol, O-pentadecyltrehalose, O-tetracosylmannitol, and branched chain alkyl sugar ether wherein the alkyl radical is derived from branched chain alkanols obtained, for example, from the 0x0 process e.g. O (oxo-tridecyl)sucrose, G-(oxo-pentadecyl)mannitol, O- (oxo-decyl)trehalose and O-(oxo-doco-syDsucrose.

Examples of O-alkenyl sugar and sugar alcohol ethers are, e.g., O-(2-dodecenyl)sucrose, O-(lO-pentadecenyl) dulcitol, O-(8-octadecenyl)sucrose, O-(3-docosenyl)raffinose, and branched chain O-alkenyl sugar and sugar alcohol ethers such as O-(5,5,7,7-tetramethyl-2-octenyl) sucrose.

Examples of O-alkarylmethyl sugar and sugar ethers prepared by the method of this invention are, e.g. O-(dodecylbenzyl)sucrose, O-(n-tridecylbenzyl)sorbitol, 0-(2- pentadecyl-l-naphthylmethyl)sucrose, and O-(4-octylxenyl)dulcitol, O-(dinonylbenzyl)sucrose, O-(tridecylethylbenzyl)sucrose, etc.

Examples of O-alkoxymethyl sugar and sugar ether compounds within the scope of this invention are, e.g., O- nonyloxymethyl sucrose, 0- (dodecyloxymethyl mannitol, O-(hexadecyloxymethyl)trehalose, O-(uncosyloxymethyl)sucrose, O-(Z-ethyloctyloxymethyl) sucrose, 0- (4, 6-diethyltetradecyloxymethyl)mannitol, and branched chain O-(alkyloxymethyl)sugar and sugar alcohol ethers wherein the branched chain alkyl portion of the compound is obtained from branched chain alkanols produced by the 0x0 process, e.g., O-(oxodecyloxymethyl)sucrose, O-(oxo-tridecyloxymethyl)dulcitol, O-(oxo-hexadecyloxymethyl) sucrose, O-(oxo-eicosyloxymethyl) sucrose, and O-(oxo-docosyloxymethyl)trehalose.

Reaction of a polyol selected from the group consisting of non-reducing disaccharide sugars and sugar alcohols, preferably sucrose, with a halide compound of the types defined above takes place readily by contacting the polyol compound with the halide compound in the presence of a basic agent, and advantageously in the presence of a dialkyl sulfoxide and agitating the resulting reaction mixture until the sugar ether product is formed. Optimum yields of sugar ether products are obtained by operating at temperatures of from about 0 C. to about 0., preferably at from about room temperature (20 C.) to about 50 C. Lower temperatures are not particularly useful because the reaction proceeds too slowly. Higher temperatures than 100 C. are not generally desired because temperatures much above this limit tend to cause sugar decomposition and also cause undesired side reactions of the halide reactant, e.g., dehydrohalogenation with resultant olefin formation. However, short periods at temperatures slightly over this upper temperature limit, e.g., to dissolve the polyol reactant in the inert solvent, may be used within the scope of this invention. Agitation of the reaction mixture also helps promote the reaction. It is preferred that the basic material used to promote the reaction between the polyol and the halide reactant be present in at least an amount stoichiometrically equivalent to the halide if the latter, i.e., the halide is the limiting reactant. For example, when sucrose is the polyol used, at least a slight excess thereof is usually present in the reaction medium since it is the cheaper reactant. The amount of basic material which is necessary to promote the reaction between the polyol and the halide reactant is that amount which is chemically equivalent to the halide reactant in the reaction medium. Examples of basic materials useful for promoting the reaction of this invention are inorganic and organic materials such as the alkali metal and alkaline earth metal hydroxides and basically reacting salts thereof, e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, as well as magnesium hydroxide, sodium acetate, and organic basic materials such as sodium methoxide, potassium ethoxide, magnesium methoxide, trimethylbenzylammonium hydroxide, etc.

Another method that may be used to provide the solution of the non-reducing polyol in the presence of a basic material for reaction with the halide reactant is to react a metal amide, e.g. sodamide or potassium amide with the polyol in ammonia to produce the metal alcoholate of the polyol. For example by dissolving an alkali metal such as sodium or potassium in liquid ammonia, generally with the aid of a metal catalyst such as trivalent iron, and then adding the polyol, the sodium or potassium sucrate is formed. The ammonia solvent must be replaced with a dialkyl sulfoxide solvent before the halide reactant is added since the halide reactants used herein do not react appreciably with sucrose or the salt thereof in the presence of ammonia.

I have found that for the reaction of this invention the selection of the proper reaction medium or diluent is important to obtain products which show good surfactant characteristics. Water alone, for example, is not a good reaction medium since the halide reactant does not readily mix with water and is usually hydrolyzed thereby. Dimethylformamide, a good polyol solvent, is not a good diluent for this reaction since in the presence of basic materials it either hydrolyzes or decomposes leaving dimethylamine which reacts adversely with the halide reactant. It is therefore, a particular embodiment of this invention to react the polyol with the alkyl, alkenyl, alkarylmethyl, or alkoxymethyl halide, as defined above, in the presence of the basic material and in the presence of a lower molecular weight dialkyl sulfoxide diluent, preferably dimethyl sulfoxide. Other lower molecular weight dialkyl sulfoxides that may be used are those having from 1 to 6 carbon atoms in each of the alkyl groups, e.g., diethyl sulfoxide, methyl ethyl sulfoxide, dipropyl sulfoxide, diamyl sulfoxide, dihexyl sulfoxide, propyl butyl sulfoxide, etc. These dialkyl sulfoxide diluents provide an excellent contact medium for the reaction of this invention. They do not react with either the sucrose or the organic halide reactant. They are good solvents for sucrose and the sucrose ether product. They may be used alone to provide an anhydrous medium which is desired in some cases, say for example, when an alkyl bromide is used as the halide reactant, the water usually being introduced into the system as an aqueous solution of the basic material which is used as the condensing agent and as a scavenger for the hydrogen halide by-product. These dialkyl sulfoxide diluents can easily be removed from the reaction product, e.g., by evaporation, vacuum distillation of the diluent, leaving the substantially pure sugar ether reaction product. A preferred method for preparing the compounds of this invention is to first dissolve sucrose in dimethyl sulfoxide, with the aid of gentle heating and stirring, then add a methanolic solution of an alkali metal or alkaline earth metal methoxide to form the salt of the alkali or alkaline earth metal and the polyol, then remove the methanol, preferably by vacuum distillation, together with a little dimethyl sulfoxide to insure complete separation of methanol before adding the alkyl, alkenyl, alkarylmethyl or alkoxymethyl halide reactant.

The preparation of the sugar-type ether products according to the method of this invention is accompanied by the formation of a hydrogen halide by-product and for that reason the reaction is advantageously efiected in the presence of a hydrogen halide scavenger, e.g., additional quantities of base. The by-product hydrogen halide is thereby converted to the salt which is readily separated from the sugar ether product by taking advan tage of solubility difference. The presently provided sugar ethers are readily soluble in the dimethyl sulfoxide diluent whereas the salt lay-product is not so soluble therein. The sugar ethers are generally soluble in lower alcohols and lower hydrocarbon liquid solvents, such as hexane, benzene, etc., and in some instances are insoluble in ether and acetone.

When the reaction is complete the reaction mixture comprises a solution of the sugar ether in the dialkyl sulfoxide diluent mixed with the basic material containing the by-product salt. The diluent as well as any unreacted sugar and salt by-product are separated from the reaction mixture by customary isolating procedures, e.g., solvent extraction, distillation, etc. Advantageously removal of any excess polyol reactant is effected by solvent extraction and the diluent by volatilization. The residue thus consists of the substantially pure ether which may be dried, e.g., by spraying, to give powdered products, or by vacuum-drying to give waxy to crystalline solids or viscous liquids depending upon the nature of the individual ether product.

The present ethers of the non-reducing disaccharide sugars or sugar alcohols are stable, usually water soluble, friable solids or gums. They are advantageously employed for a variety of industrial purposes and are particularly valuable as surfactants. Some of the sugar ethers possess biological toxicant properties and others, particularly those which are gums at ordinary temperatures, are valuable as modifiers for synthetic resins and plastics and as textile adjuvants, e.g., as softening and antistatic agents.

The present invention is further illustrated by, but not limited to the following examples:

Example 1 To 250 ml. of dimethyl sulfoxide there was added 51.3 g. (0.15 mole) of sucrose and the mixture was heated gently with agitation to dissolve the sucrose. After cooling the sucrose solution to 40 C., 29.2 g. (0.10 mole) of dodecylbenzyl chloride was added while continuing to stir the mixture. Then 12.3 g. (0.11 mole) of 50% potassium hydroxide diluted in 40 ml. of water was added as the mixture was heated to 65 C. during 0.75 hour. The resulting reaction mixture was then extracted with Skellysolve F (a mixture of C -C parafiins, B.P. 3050 C./atrn. pressure) to give a nearly clear lower dimethyl sulfoxide layer containing the product unchanged sucrose and inorganic salts, and an upper layer containing oily lay-products and unreacted dodecylbenzyl chloride. The layers were separated and the dimethyl sulfoxide layer was concentrated with stirring below 75 C. under oil pump vacuum to remove the dimethyl sulfoxide, leaving a thick syrupy residue which was poured into about 600 ml. of isopropyl alcohol in a Waring Blender. The precipitated sucrose was removed by filtration and washed on the filter with isopropanol. The combined washings and filtrates were concentrated below 75 C, finally at 0.4 mm, leaving 20.5 g. of a clear nearly colorless gum, substantially dodecylbenzylsucrose.

Example 2 To a solution of 68.4 g. (0.20 mole) of sucrose dissolved in 200 ml. of (ii-methyl sufoxide with the aid of gentle heating and then cooled to 40 C. there was added 10.0 g. (0.1 mole) of 40% sodium hydroxide diluted to 30 ml. with Water. Then 20.3 g. (0.1 mole) of dodecenyl chloride was added drop-wise. The resulting mixture was then heated while stirring to 73 C. for about 2.5 hours. During this time samples of the reaction mixture were extracted and tested in water to determine lathering activity. The samples showed increasing l-athering activity but remained slightly turbid. The reaction mixture was then extracted with hexane, leaving a lower separate layer of the di-methyl sulfoxide and product. The dimethyl sulfoxide-product layer was separated from the hexane, and distilled under vacuum up to 70 C./1 mm, to remove the dimethyl suli'oxide. The residue product was purified by pouring it hot into 600 ml. of isopropyl alcohol in a Waring Blendor, filtering ofi the excess sucrose, and finally distilling ofi the alcohol and residual dimethyl sulfoxide up to 100 C. /1 leaving 43.8 'g. a hard, resinous gum (brittle in Dry Ice), crude dodecenylsucrose.

For use in Examples 3 and 4 the following solution was prepared:

Sucrose (102.7 ig.0.3 mole) was dissolved in 400 ml. of dimethyl sulfoxide by warming the mixture with stirring until solution occurred. Then at 70 C. with good stirring 25% methanolic sodium methoxide (11.9 g.0.22 mole of sodium methoxide in 47.6 g. of solution) was added dropwise over a two hour period. Another 100 ml. of dimethyl su'lfoxide was added and then the methanol was removed under aspirator vacuum to C. The resulting solution, 644.2 g. was divided into two equal parts for the following two examples.

Example 3 While stirring 322.1 g. of the above prepared solution (thus containing 0.15 mole of sucrose and 0.11 mole of sodium equivalent in dimethyl sulfoxide) at 40 C., 37.8 g. 0.1 mole) of octadecylbenzyl chloride was added dropwise during 35 minutes. The mixture was stirred and heated at 4045 C. for 6 hours and then the stirring was continued for 10 additional hours at ambient temperatures. The resulting reaction mixture was extracted with hexane to remove oils. The dimethyl sulfoxide-product phase was separated and distilled up to 65 C./0.8 mm. to remove the dimethyl sulfoxide leaving a thick syrup which was poured hot into excess isopropyl alcohol in a Waring Blendor and filtered to remove the excess unreacted sugar. The isopropyl alcohol was distilled off under vacuum leaving 19.5 .g. of brittle, amber resin, octadecylbenzylsuorose.

Example 4 To 322.1 g. of a dimethyl sulfoxide solution containing 0.15 mole of sucrose and 0.11 mole of sodium equiva 7 lent prepared as indicated above there was added, while stirring and heating to 3540 C., 20.3 g. (0.1 mole) of dodecenyl chloride over 0.5 hour. The resulting reaction mixture was then treated in the same manner as that described in Example 3 above. There was obtained 35.5 g. of an amber viscous gum, dodecenylsucrose.

Example 5 To a solution consisting of 51.3 g. (0.15 mole) of sucrose in 250 ml. of dimethyl sulfoxide, warmed to 70 C.-80 C., there was added 25.9 g. (0.11 mole) of a 25% sodium methoxide in methanol solution, while stirring. An additional 50 ml. of dimethyl sulfoxide was added when the mixture became turbid. The methanol and about 50 ml. of the dimethyl sulfoxide were removed at 5070 C. first under aSpir-ator vacuum and then under pump vacuum to 1 mm. To the resulting residual translucent solution there was added 26.3 g. (0.10 mole) of n-tridecyl bromide at 45 C. in minutes. The mixture was stirred for three hours during which time samples were extracted and tested in water to determine lather activity and turbidity. At the end of the three hours, the material showed very good lather activity with no improvement thereafter. The reaction mixture was extracted with hexane, distilled to remove dimethyl sulfoxide to 80 C. at 0.1 mm., then the residual syrup poured into 600 ml. isopropanol in the Waring Blendor and filtered to remove sucrose and inorganics. After again extracting the filter cake with isopropanol and evaporating the filtrates, there was obtained 30.9 g. of clear, slightly yellow resinous n-tridecylsucrose.

A solution of 257 g. (0.75 mole) of sucrose in 1250 ml. of dimethyl sulfoxide was made by warming and stirring the sucrose and dimethyl sulfoxide. 70 C.-80 C. this solution was treated with 108 g. (0.50 mole) of a sodium methoxide in methanol solution. The mixture was stirred well and then the methanol was removed under the aspirator vacuum to 80 C. and then together with about 200 ml. of dimethyl sulfoxide at 70 C./1 mrn., leaving 1449 g. of a nearly clear solution with little suspended insolubles, containing approximately 0.50 mole of sodium sucrate and 0.25 mole of excess unreacted sucrose. This solution was divided for the following examples.

Example 6 tilled at reduced pressure and the residue was extracted with isopropanol to remove the product from the sucrose which is nearly insoluble in isopropanol. The isopropanol Was distilled off under vacuum to leave 33.7 g. of oxo-decylsucrose (69.8% yield) as an amber hard gum.

Example 7 To 319 g. of the dimethyl sulfoxide solution of sucrose and sodium sucrate prepared as above, 26.3 g. of 0x0- tridecyl bromide was added. The mixture was sealed in a reaction flask and shaken for 42 hours. An oil layer which remained was extracted into hexane, and then the dimethyl sulfoxide solvent was distilled under vacuum up to 80 C./0.1 mm. The syrupy residue was poured into 600 ml. of ethyl alcohol in a Waring Blendor, mixed as usual, and filtered to remove unreacted sucrose. The solution was distilled to remove alcohol and some dimethyl sulfoxide that remained. The residue was triturated with hot isopropanol to precipitate more sucrose,

cooled and refiltered. The isopropanol filtrate contain- Then at 8 ing dissolved product was distilled under vacuum to C./1 mm. leaving 35.8 g. (68% yield) of a clear amber hard resinous gum (oxo-tridecylsucrose) which showed good lathering activity in water.

Example 8 To 174 g. of the solution of sodium sucrate in dimethyl sulfoxide prepared as above there was added 15.3 g. of oxo-hexadecyl bromide. The mixture was shaken at room temperature for three days. The resulting reaction mixture was treated as in Example 7 above to isolate the product. There was obtained 14.0 g. of a very viscous gum, xo-hexadecylsucrose product.

Example 9 To 319 g. (0.11 mole) of sodium sucrate in dimethyl sulfoxide prepared as above, 24.9 g. (0.10 mole) of, Z-butyloctyl bromide was added. The mixture was shaken for 7 days. Activity of a sample of the reaction mixture in water as a lathering agent was noted after 1 day. Further agitation did not increase the activity of the product. The resulting reaction mixture was treated as in Example 7 to separate and purify the product. There was obtained 12.0 g. of a hard gum, (2-butyloctyl)- sucrose.

Example 10 To 319 g. of the solution of sodium sucrate in dimethyl sulfoxide prepared as above, there was added 23.2 g. of n-tetradecyl chloride. The mixture was stirred at room temperature for 7 days. A sample of the reaction mixture showed little activity in water so the mixture was heated at 50 C. for 16 hours with stirring. The mixture was cooled and then treated as in Example 7 to separate and purify the product. There remained as product, 3.0 g. of an amber gum, n-tetradecyisucrose, which was completely soluble in water and which had good lather activity.

Example 11 To a solution of 120 g. (0.35 mole) of sucrose dissolved in 600 ml. of dimethyl sulfoxide with the aid of gentle heating and stirring, there was added 66.9 g. of a 25% by weight solution of sodium methoxide in methyl alcohol (16.7 g. of sodium methoxide, 0.31 mole). The mixture was heated While stirring to C./0.5 mm. to remove the methanol and some dimethyl sulfoxide. The final suspensionsolution weighed 710 g. and contained approximately 0.31 mole of sodium sucrate.

To a 304 g. portion of this solution, cooled to about 18 0., 24.9 g. (0.110 mole) of chloromethyl oxo-tridecyl ether was added at once and mixed. The temperature rose spontaneously to 35 C. The mixture was rapidly cooled to 25 C., sealed and shaken for 16 hours. The reaction mixture was extracted with hexane to remove the oils, the product-dimethyl sulfoxide mixture was separated therefrom, and distilled under vacuum to remove the dimethyl sulfoxide. The residue product was washed in isopropyl alcohol in a Waring Blendor, filtered, and distilled to remove the alcohol solvent up to 80 C./ 0.2 mm. There remained as product 20.7 g. of a hard resin, (oxo-tridecyloxymethyl)sucrose which showed good activity as a detergent and as a lime soap dispersant.

Example 12 Sucrose (68.4 g., 0.20 mole) was added to 200 ml. of dimethyl sulfoxide and dissolved with aid of gentle stirring and heating to 65 C. After cooling the solution to room temperature 15 g. of 40% sodium hydroxide diluted with 15 ml. of water was added and then 29.5 g. (0.10 mole) of dodecylbenzyl chloride was added. The mixture was'stirred at 30 C., 15 ml. more water was added and then the mixture was gradually heated to 70 C. over a 1. hour period. Samples of the reaction mixture taken during this time showed increasing lather activity in water. After an additional hour of stirring the reaction mixture at 70 C., no increase in lather activity was obtained; to the hot mixture 200 ml. of hexane was added, the mixture was shaken, and the layers separated. The dimethyl sulfoxide layer was then distilled and the residue treated with isopropanol in a Waring Blendor, filtered to remove sucrose, and the liltrate evaporated to dryness up to 80 C./1 mm. leaving 16.1 g. of substantially pure dodecylbenzylsucrose.

Example 1 3 .dirnethyl sulfoxide and poured hot into isopropanol.

After filtering and drying as in the prior example there was obtained 48.2 g. of dodecylbenzylsucrose.

The dodecylbenzylsucrose ethers obtained by the methods used in each of Examples 12 and 13 were given the best lime soap dispersion ratings obtainable (dispersion number of according to the lime soap dispersion test described by J. C. Harris in Evaluation of Surface Active Agents, cited infra.

Example 14 Sucrose (51.3 g.) was dissolved in 250 ml. of dimethylformamide and warmed to 70 C. to 75 C. at which temperature 23.7 g. of by weight, sodium methoxide in methanol solution (equivalent to 0.11 mole as sodium methoxide) was added dropwise. A white solid precipitated but was dispersed by stirring the mixture. Methanol and some dimethylformamide were removed by heating under aspirator vacuum. To the remaining solution 26.3 g. of oxo-tridecyl bromide was added all at once. The mixture was stirred and heated at 68 to 84 C. for 4 hours during which time samples of the reaction mixture were periodically extracted and tested for lather activity and turbidity. Only slight activity was noted after the full 4 hour period. The reaction mixture was cooled and extracted with about 150 ml. of hexane. A solid precipitated but did not interfere with the extraction. The hexane layer was separated from the dirnethylformamide layer. The dimethylformamide layer including the solid precipitate was distilled at 75 C./aspirator vacuum to remove most of the dimethylformamide. The syrupy residue was poured hot into about 5 00 ml. of isopropanol in a Waring Blendor, the sucrose, was filtered off, and then the clear isop'ropanol filtrate was evaporated to dryness leaving 22.9 g. (43.7% yield if pure oxo-tridecylsucrose) of a residue which was evaluated for detergency value. The results are given in the table below.

In a test taken from Detergency, Evaluation and testing, by I. C. Harris, interscience publication (1954) p. 9297, using Gardinol (Duponol WA-Dupont; produced by sulfating a mixture of alcohols, principallyC obtainable by hydrogenation of coconut oil fatty'acids) as a standard detergent, having an arbitrary detergency rating of 100, several compounds of the present invention were tested as received, that is without being compounded into a detersive composition, in water having parts per million (ppm) hardness at C., against Gardinol under the same conditions. The results were as follows.

Detersive rating Product of Example 14 When these sucrose ethers were compounded into built detergent compositions comprising 15% by weight of the sucrose ether, 40 parts by weight of a mixture ofsodium tripolyphosphate and sodium tetrapyrophosphate, 20% soda ash, and 25% sodium silicate, and tested in water of 50 ppm. hardness at 60 C. against Gardinol which was compounded and tested in identical manner, the detersive ratings of these sucrose ethers were as follows.

Detersive rating in Ether: water, 50 ppm. Oxo-decylsucrose Oxo-tridecylsucrose 137 Oxo-hexadecylsucrose 132 (2-butyloctyl)sucrose 116 The following sucrose ethers, compounded into the built detergent compositions, as indicated above, were also tested in waters of 300 ppm. hardness at 60 0, against Gardinol as a standard, compounded and tested in an identical manner, with the following results:

Product of Example 14 Detersive rating in Ether: Water, 300 ppm. n-Tridecylsucrose 149 Oxo-tridecylsucrose 141 Oxo-hexadecylsucrose 122 Product of Example 14- 33 Of the sucrose ethers tested above, oxo-tridecylsucrose and oxo-hexadecylsucrose were each found to have good lime soap dispersion properties, having dispersion numbers of 20 according to the lime soap dispersion test described by J. C. Harris in Evaluation of Surface Active Agents, in American Society for Testing Materials (ASTM) Bulletin, No. 140, May 1946.

The new ether compounds of this invention are very soluble in Water. They may be used alone in water as wetting and detergent materials. They are particularly water soluble in the presence of inorganic builders used in making detergent compositions. They are especially valuable in soap compositions as lime soap dispersants. In detergent compositions generally they are valuable as detergent materials having the characteristic of being biodegradable by microorganisms in sewage, sludge, and water treatment plants. Useful detergent compositions can be formed by mixing small proportions of soap with large proportions of the ethers of this invention. Usually, however, it is preferred to incorporate into the soap composition about 5 to 50% by weight of the ether compound based on the total weight of the soap containing detergent composition. Of course, other materials such as fillers, inorganic builders, of the'type such as carbonates, phosphates, and silicates, perfume, pigments, etc., can also be present in the composition.

The soaps which are useful in the novel compositions of this invention are the so-called water-soluble soaps of the soapmaking art and include sodium, potassium, ammonium, and amine salts of the higher fatty acids, i.e., those having from about 8 to 20 carbon atoms per molecule. These soaps are normally prepared from such naturally occurring esters as coconut oil, palm oil, olive oil, fat, tallow whale oil, and the like, as well as mixtures of these.

A typical preparation of bar stock composition using one of the ethers of this invention as an ingredient therein is illustrated by the following example.

Example 15 To minimize quantities used a Carver press and die are used to provide bars about 2 /2 inches in diameter and about /2 inch thick. The raw materials, listed below are well mixed mechanically, then passed through a 3-roll ink mill to further mix the ingredients, the resulting flakes are transferred to the die and pressed into discs. The ingredients compounded and their relative parts by weight .5. based on the total weight of the composition are listed in the following formula.

Water The water content is varied as required for adequate working characteristics.

Reasonable variation and modification of the invention as described are possible, the essence of which is that there have been provided (1) new alkyl, alkenyl, alkoxymethyl, and alkaryhnethyl ethers of non-reducing disaccharide polyols, (2) methods for making alkyl, alkenyl, alkoxymethyl, and alkarylmethyl ethers of non-reducing disaccharide polyol sugar-type ethers (3) said sugar type ethers as the biodegradable surface active ingredient in compositions comprising a sodium, potassium, or ammonium long-chain fatty acid soap and said sugar-type ethers.

What is claimed is:

1. Compounds of the formula R-CH -sucrose wherein R is selected from the group consisting of alkyl radicals, alkenyl radicals having the olefinic double bond beyond the alpha position relative to the ether oxygen atom, and alkyloxy radicals having from 8 to 24 carbon atoms, and alkaryl radicals having a total of from 14 to 24 carbon atoms and from 8 to 18 carbon atoms in at least one alkyl radical attached to the aryl ring, and the sucrose is linked to the methylene group through the oxygen atoms of one of the hydroxyl groups of the sucrose.

2. Compounds as described in claim 2 wherein R is an alkyl radical having from 8 to 24 carbon atoms.

3. Compounds as described in claim 1 wherein R is an alkenyl radical having the olefinic double bond beyond the alpha position relative to the ether oxygen atom and having from 8 to 24 carbon atoms.

4. Compounds as described in claim 1 wherein R is an alkyloxy radical having from 8 to 24 carbon atoms.

5. Compounds as described in claim 2 wherein R is an alkylaryl radical having a total of from 14 to 24 carbon atoms and having from 8 to 18 carbon atoms in at least one alkyl radical attached to the aryl ring.

6. O-oxo-decylsucrose.

7. O-n-tridecylsucrose.

8. O-(oxo-tridecyloxymethyl)sucrose.

9. O- (dodecylbenzyl sucrose.

10. O-dodecenylsucrose.

11. The method of preparing a sucrose ether which comprises reacting sucrose with a compound of the formula R-CH -X wherein X is a halogen atom selected from the group consisting of bromine, chlorine, and iodine, and R is selected from the group consisting of alkyl radicals, alkenyl radicals having the olefinic double bond beyond the alpha position relative to the halogen atom and alkoxyl radicals having from 8 to 24 carbon atoms, and alkaryl radicals having a total of from 14 to 24 carbon atoms and from 8 to 18 carbon atoms in at least one alkyl group attached to the aryl ring, in the presence of a basic material and a dialkyl sulfoxide diluent in which the two alkyl radical of the dialkyl sulfoxide each have from 1 to 6 carbon atoms at a temperature of from about 0 C. to about C.

12. The method of claim 11 wherein R is a branched chain alkyl radical having from 8 to 24 carbon atoms, and X is bromine.

13. The method of claim 11 wherein R is an alkenyl radical having from 8 to 24 carbon atoms and X is chlorine.

14. The method of claim 11 wherein R is an alkoxyl radical having from 8 to 24 carbon atoms, and X is chlorme.

15. The method of claim 11 wherein R is an alkaryl radical having from 14 to 24 carbon atoms and from 8 to 18 carbon atoms in at least one alkyl radical attached to the aryl ring, and X is chlorine.

16. The method which comprises reacting sucrose with sodium methoxide in the presence of dimethyl sulfoxide to produce sodium sucrate, reacting the resulting sodium sucrate with a compound of the formula wherein X is a halogen selected from the group consisting of bromine, chlorine, and iodine, and R is selected from the group consisting of alkyl radicals, alkenyl radicals having the olefinic double bond beyond the alpha position relative to the halogen atom, and alkoxyl radicals having from 8 to 24 carbon atoms, and alkaryl radicals having a total of from 14 to 24 carbon atoms and having from 8 to 18 carbon atoms in at least one alkyl group attached to the aryl ring, at a temperature of from about 0 C. to about 100 C. and recovering from the resulting reaction mixture a compound having the formula RCH -sucrose wherein R is as defined above, and the sucrose is linked to the methylene group through the oxygen atom of one of the hydroxyl groups of the sucrose.

References Cited in the file of this patent UNITED STATES PATENTS Re. 23,443 Lolkema Dec. 18, 1951 1,504,178 Young Aug. 5, 1924 1,936,093 Lawson Nov. 21, 1933 2,258,171 Barry Oct. 7, 1941 2,543,744 Fox Mar. 6, 1951 2,585,035 Roach et a1 Feb. 12, 1952 2,719,970 Griffin et a1. Oct. 4, 1955 2,875,153 Dalton Feb. 24, 1959 2,938,898 Werner et a1. May 31, 1960 2,974,134 Pollitzer Mar. 7, 1961 OTHER REFERENCES Arni et a1.: Jour. Applied Chem., vol. 9, March 1959, pp. 186-189.

Black et a1.: Jour. Applied Chem, vol. 9, May 1959, pp. 256-261. 

1. COMPOUNDS OF THE FORMULA 